CN111430485B - Preparation method of high-adhesion barrier layer for stainless steel substrate copper indium gallium selenide solar cell - Google Patents
Preparation method of high-adhesion barrier layer for stainless steel substrate copper indium gallium selenide solar cell Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 61
- 239000010935 stainless steel Substances 0.000 title claims abstract description 55
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 55
- 230000004888 barrier function Effects 0.000 title claims abstract description 25
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 17
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 10
- 238000001020 plasma etching Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000004544 sputter deposition Methods 0.000 claims abstract description 5
- 238000002211 ultraviolet spectrum Methods 0.000 claims abstract description 5
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 150000004767 nitrides Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal nitride Chemical class 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- H—ELECTRICITY
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02162—Coatings for devices characterised by at least one potential jump barrier or surface barrier for filtering or shielding light, e.g. multicolour filters for photodetectors
- H01L31/02164—Coatings for devices characterised by at least one potential jump barrier or surface barrier for filtering or shielding light, e.g. multicolour filters for photodetectors for shielding light, e.g. light blocking layers, cold shields for infrared detectors
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- H01—ELECTRIC ELEMENTS
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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Abstract
The invention discloses a preparation method of a high-adhesion barrier layer for a stainless steel substrate copper indium gallium selenide solar cell, belonging to the technical field of copper indium gallium selenide solar cells and comprising the following steps: firstly, ultrasonically cleaning a stainless steel substrate by acetone, alcohol and pure water in sequence, wherein the cleaning time is 15 minutes each time, and drying the stainless steel substrate by using nitrogen for later use; secondly, carrying out high-energy plasma etching treatment on the stainless steel substrate, wherein the working pressure of an etching machine is 4 multiplied by 10 < -2 > Pa, the power is 0.4 KW-0.8 KW, and the etching time is 20 minutes; thirdly, putting the stainless steel substrate into an ultraviolet irradiation box, wherein the wavelength range of an ultraviolet spectrum is as follows: 185-254 nm, power 150W and time 40 min; fourthly, preparing the 0.5-1.5 micron aluminum nitride or titanium nitride barrier layer by adopting a magnetron sputtering method, wherein the working pressure is 0.3Pa, the power is 0.6 KW-1.0 KW, and the sputtering time is 35-45 minutes.
Description
Technical Field
The invention belongs to the technical field of copper indium gallium selenide solar cells, and particularly relates to a preparation method of a high-adhesion barrier layer for a stainless steel substrate copper indium gallium selenide solar cell.
Background
In recent years, serious environmental pollution caused by the rapid development of economy becomes one of the important problems facing the development of the current society. The massive use of fossil energy is one of the root causes of environmental pollution. Based on this, people pay more and more attention to the use of renewable clean energy. Solar energy has many advantages of being clean, renewable, inexhaustible, and the like, and is becoming an important choice for solving energy crisis and environmental crisis, wherein the solar cell (photovoltaic) mode is most directly utilized.
The solar cell technology has been developed to date, and various solar cells such as silicon-based solar cells (single crystal silicon, polycrystalline silicon), compound thin film solar cells (gallium arsenide, copper indium gallium selenide, cadmium telluride, etc.), and solar cells using organic materials (organic, dye-sensitized, perovskite, etc.) have been formed. The thin film solar cell has a wide application prospect due to the advantages of high absorption coefficient, less raw materials, application of large-scale preparation processes such as roll-to-roll and the like, flexibility and the like, wherein the Copper Indium Gallium Selenide (CIGS) thin film solar cell has the best industrialization prospect. In order to highlight the characteristics of light weight and flexibility of the copper indium gallium selenide thin-film solar cell, more and more research institutions and companies develop a preparation process research based on ultrathin stainless steel (the thickness is less than 50 micrometers) as a substrate. The stainless steel substrate contains Fe element, which can diffuse into the CIGS absorption layer in the subsequent high-temperature coating process, so that adverse effect is brought, and the photoelectric conversion efficiency of the battery is greatly reduced. Therefore, in order to prevent Fe from diffusing from the substrate to the thin film, one generally prepares a barrier film on the substrate surface, and the structure of the conventional copper indium gallium selenide thin film solar cell based on a stainless steel substrate is shown in fig. 1.
To summarize the barrier layer materials used at present, there are mainly Cr (shown in patent application No. 201210054329.7), aluminum nitride (shown in patent application No. 201210027169.7), molybdenum nitride (shown in patent application No. 201620807205.5), silicon oxynitride (shown in patent application No. 201621249997.5), transition metal nitride or transition oxynitride (shown in patent application No. 201510759999.2), tungsten-titanium alloy (shown in patent application No. 201410395198.8), and the like. However, the diffusion of Cr element into the CIGS absorbing layer exists when Cr or other metals are used as the substrate barrier layer, the performance of the battery is also deteriorated, the bonding force between the barrier layer and the substrate is insufficient when metal nitrides, oxides or composite multilayer structures thereof and the like are used, and the film falls off due to chemical solution soaking in the subsequent coating process, particularly in the process of preparing the CdS buffer layer by adopting a chemical water bath method, so that the overall preparation of the battery is influenced.
Disclosure of Invention
The invention provides a preparation method of a high-adhesion barrier layer for a stainless steel substrate copper indium gallium selenide solar cell, which aims at solving the technical problems that the traditional nitride and oxide substrate barrier layer has poor adhesion and the subsequent coating film is easy to fall off (particularly in the process of depositing a CdS buffer layer in a water bath), solves the problem of poor adhesion of the barrier layer, provides a good foundation for preparing a high-efficiency copper indium gallium selenide solar cell, and finally realizes the improvement of the photoelectric conversion efficiency of the cell.
The invention aims to provide a preparation method of a high-adhesion barrier layer for a stainless steel substrate copper indium gallium selenide solar cell, which comprises the following steps:
s1, carrying out ultrasonic cleaning on the stainless steel substrate by acetone, alcohol and pure water in sequence, wherein the cleaning time is 15 minutes each time, and drying the stainless steel substrate by using nitrogen for later use;
s2, putting the stainless steel substrate into a plasma etching machine for high-energy plasma etching treatment, wherein the working pressure of the etching machine is 4 multiplied by 10 < -2 > Pa, the power is 0.4 KW-0.8 KW, and the etching time is 20 minutes;
s3, placing the stainless steel substrate into an ultraviolet irradiation box, wherein the wavelength range of an ultraviolet spectrum is as follows: 185-254 nm, power 150W and time 40 min;
s4, putting the stainless steel substrate into a magnetron coating system, and preparing a 0.5-1.5 micron aluminum nitride or titanium nitride barrier layer by adopting a magnetron sputtering method, wherein the working air pressure is 0.3Pa, the power is 0.6 KW-1.0 KW, and the sputtering time is 35-45 minutes.
Further, the stainless steel substrate is a SUS304 or SUS430 type stainless steel substrate.
Still further, the stainless steel substrate has a thickness of no greater than 50 microns.
Further, the S1 is specifically: firstly, cutting a stainless steel substrate according to requirements, and then carrying out ultrasonic cleaning and air drying on acetone, alcohol and pure water in sequence.
Further, the stainless steel substrate has a size of 10cm × 10 cm.
The invention has the advantages and positive effects that:
the invention develops a film surface treatment process of plasma and ultraviolet light bath, strong ultraviolet light can decompose water molecules in the air, and hydroxyl groups are enriched on the surface of the substrate, so that the substrate is in a hydrophilic characteristic, and the adhesion between a subsequent coating film and the substrate is improved. The process can greatly improve the adhesive force between the barrier layer and the stainless steel substrate, so that the overall mechanical performance of the copper indium gallium selenide solar cell is improved, the improvement of the overall mechanical performance of the film layer can reduce the series resistance of a cell device, so that the electrical performance of the cell device is improved, and finally the photoelectric conversion efficiency of the cell is improved by over 10 percent through test.
Drawings
Fig. 1 is a structure of a conventional copper indium gallium selenide thin-film solar cell based on a stainless steel substrate;
fig. 2 is a flow chart of a preferred embodiment of the present invention.
Detailed Description
For a further understanding of the invention, its nature and utility, reference should be made to the following examples, taken in conjunction with the accompanying drawings, in which:
as shown in fig. 2, the technical solution of the present invention is:
a method for preparing a high-adhesion barrier layer for a copper indium gallium selenide solar cell with a stainless steel substrate is based on an SUS304 or SUS430 type stainless steel substrate with the thickness of 50 microns (or less). Firstly, ultrasonically cleaning a cut stainless steel substrate by acetone, alcohol and pure water in sequence, wherein the cleaning time is 15 minutes each time, and drying the stainless steel substrate by using nitrogen for later use. Then, the stainless steel substrate is put into a plasma etching machine for high-energy plasma etching treatment, the working pressure of the etching machine is 4 multiplied by 10 < -2 > Pa, the power is 0.4KW to 0.8KW, and the etching time is 20 minutes, so that an oxide layer on the surface of the stainless steel is removed. Next, the etched stainless steel substrate is placed in an ultraviolet irradiation box, and the wavelength range of the ultraviolet spectrum is as follows: 185-254 nm, power 150W and time 40 minutes, aiming at removing carbon and oxygen residues on the surface of the film. And finally, putting the treated stainless steel substrate into a magnetron coating system, and preparing a 0.5-1.5 micron aluminum nitride or titanium nitride barrier layer by adopting a magnetron sputtering method, wherein the working air pressure is 0.3Pa, the power is 0.6 KW-1.0 KW, and the sputtering time is 35-45 minutes. The stainless steel substrate barrier layer prepared by the method has good adhesive force and obvious barrier effect on Fe element. The process sequence of cleaning and post-treatment (plasma etching and ultraviolet light irradiation) cannot be changed.
A10 cm × 10cm 50 μm model SUS430 stainless steel substrate was cut. And (2) carrying out ultrasonic cleaning on the stainless steel substrate by acetone, alcohol and pure water in sequence, wherein the cleaning time is 15 minutes each time, and drying the stainless steel substrate by using nitrogen for later use. Then, the stainless steel substrate is put into a plasma etching machine for high-energy plasma etching treatment, the working pressure of the etching machine is 4 multiplied by 10 < -2 > Pa, the power is 0.6KW, the etching time is 20 minutes, and the oxide layer on the surface of the stainless steel is removed. Next, the etched stainless steel substrate is placed in an ultraviolet irradiation box, and the wavelength range of the ultraviolet spectrum is as follows: 185-254 nm, power 150W, time 40 minutes, removing the carbon and oxygen residue on the film surface. And finally, putting the treated stainless steel substrate into a magnetron coating system, and preparing an aluminum nitride barrier layer with the thickness of 1 micron by adopting a magnetron sputtering method, wherein the working air pressure is 0.3Pa, the power is 0.6KW, and the sputtering time is 40 minutes.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (4)
1. A preparation method of a high-adhesion barrier layer for a stainless steel substrate copper indium gallium selenide solar cell is characterized by comprising the following steps: the method comprises the following steps:
s1, ultrasonic cleaning the stainless steel substrate with acetone, alcohol and pure water in sequence, wherein the cleaning time is 15 minutes each time, and drying the stainless steel substrate with nitrogen for later use; the stainless steel substrate is an SUS304 or SUS430 type stainless steel substrate;
s2, putting the stainless steel substrate into a plasma etching machine for high-energy plasma etching treatment, wherein the working pressure of the etching machine is 4 multiplied by 10 < -2 > Pa, the power is 0.4 KW-0.8 KW, and the etching time is 20 minutes;
s3, placing the stainless steel substrate into an ultraviolet irradiation box, wherein the wavelength range of an ultraviolet spectrum is as follows: 185-254 nm, power 150W and time 40 min;
s4, putting the stainless steel substrate into a magnetron coating system, preparing a 0.5-1.5 micron aluminum nitride or titanium nitride barrier layer by adopting a magnetron sputtering method, wherein the working pressure is 0.3Pa, the power is 0.6 KW-1.0 KW, and the sputtering time is 35-45 minutes.
2. The method for preparing the high-adhesion barrier layer for the stainless steel substrate CIGS solar cell according to claim 1, wherein the thickness of the stainless steel substrate is not more than 50 μm.
3. The method for preparing the high-adhesion barrier layer for the stainless steel substrate CIGS solar cell according to claim 2, wherein S1 specifically comprises: firstly, cutting a stainless steel substrate according to requirements, and then carrying out ultrasonic cleaning and air drying on acetone, alcohol and pure water in sequence.
4. The method for preparing the high-adhesion barrier layer for the stainless steel substrate CIGS solar cell according to claim 1, wherein the dimension of the stainless steel substrate is 10cm x 10 cm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165923A (en) * | 2006-10-19 | 2008-04-23 | 中国电子科技集团公司第十八研究所 | Flexible copper-indium-gallium-selenium film solar cell and its preparation method |
| CN101294272A (en) * | 2008-05-27 | 2008-10-29 | 浙江大学 | Method for sputtering and depositing tin indium oxide transparent electroconductive film on flexible substrate at room temperature |
| CN103235353A (en) * | 2013-04-18 | 2013-08-07 | 中国科学院长春光学精密机械与物理研究所 | Processing method for enabling deep ultraviolet film having optical stability |
| CN108374153A (en) * | 2018-01-17 | 2018-08-07 | 南京大学 | A kind of Grown by Magnetron Sputtering large area, the method for high-sequential nano particle |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165923A (en) * | 2006-10-19 | 2008-04-23 | 中国电子科技集团公司第十八研究所 | Flexible copper-indium-gallium-selenium film solar cell and its preparation method |
| CN101294272A (en) * | 2008-05-27 | 2008-10-29 | 浙江大学 | Method for sputtering and depositing tin indium oxide transparent electroconductive film on flexible substrate at room temperature |
| CN103235353A (en) * | 2013-04-18 | 2013-08-07 | 中国科学院长春光学精密机械与物理研究所 | Processing method for enabling deep ultraviolet film having optical stability |
| CN108374153A (en) * | 2018-01-17 | 2018-08-07 | 南京大学 | A kind of Grown by Magnetron Sputtering large area, the method for high-sequential nano particle |
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